Acetals containing epoxide groups



United States Patent 3,210,375 ACETALS CONTAINKNG EPQX'IDE GROUPS Daniel Porret, Basel, Willy Fisch, Binningen, Hans Batzer, Arlesheim, and Otto Ernst, Pfeifingen, Switzerland, assignors to Ciba Limited, Basel, Switzerland, a company of Switzerland N0 Drawing. Filed July 10, 1964, Ser. No. 381,884 Claims priority, application Switzerland, Sept. 10, 1959, 78,068/59 3 Claims. (Cl. 260-3405) This is a continuation-in-part of our application Ser. No. 54,581, filed September 8, 1960, now Patent No. 3,072,678, issued January 8, 1963.

The present invention provides new acetals which contain at least two epoxide groups and correspond to the in which X, .and X each represent a hydrogen atom or a methyl group; Z represents an organic radical containing at least one epoxide group; H. is a small whole number, and Y represents the radical of .a polyhydric alcohol with 20 free valences and, when n=l, the radical Y must contain at least one epoxide group.

The new acetals are obtained by the present process when:

(A) An acetal, which contains at least one epoxidizable group, of the formula --in which X X and n have the same meanings as in Formula I; Z represents an organic radical which contains at least one epoxide group or an epoxidizable group; and Y represents the radical of a polyhydric alcohol with 2n free valences and, when n='1, the radical Y must contain at least one epoxide group or epoxidizable groups-As treated with an epoxidizing agent; or

(B) n Mols of a compound of the formula Z.OH are added on to one mol of an unsaturated acetal of the formula- Y CHO=CH Ii l l l -0 X1 X2 (III) Hi) I IaI (in which Hal represents a halogen atom), such as a ,8- methyl-glycerol-ot-monochlorohydrin radical or a glycerol a-monochlorohydrin radical. As is known, such a halohydrin group can likewise be converted into a 1:2 epoxide group by treatment with a dehydrohalogenating agent.

The acetals of the Formula II or III to be used as starting materials in the present process are obtained most 3,210,375 Patented Oct. 5, 1965 readily by acetalizing methacrolein or preferably crotonic aldehyde or acrolein with the dialcohol or polyalcohol.

In this connection two cases have to be distinguished;

(1) The polyalcohol used contains as such at least one unsaturated group which can be directly epoxidized in a second stage or after an additive reaction with an alcohol of the formula ZOH or Z'-OH can be converted into an epoxy compound. In this case there may be used polyalcohols containing at least two hydroxyl groups.

(2) The polyalcohol is free from double bonds, in which case it must contain at least four hydroxyl groups.

In case (1) there may be mentioned as unsaturated polyalcohols, for example:

Butene-(2)-diol-1:4, glycerol monoallyl ether, butanetriol-(1:2:4)-monoallyl ether and the like, furthermore above all dialcoho-ls of the formula (I in which R to R each represent monovalent substituents, such as halogen atoms, alkoxy groups or aliphatic, cycloaliphatic, araliphatic or aromatic hydrocarbon radicals, more especially alkyl radicals with 1 to 4 carbon atoms, or hydrogen atoms, wherein R and R together may also represent an alkylene radical, such as a methylene group. As examples of such dialcohols IV there may be mentioned:

1: l-bis-[hydroxymethyl] cyclohexene (3), 1:1 bis- [hydroxymethyl]-6-methylcyclohexene-(3), 1:1-bis [hydroxymethyl]-2:4:6-trimethylcyclohexne (3), 1:1 bis: [hydroxymethyl]-2:5-endomethylene cyclohexene (3) and 1 l-bis- [hydroxymethyl] -4-chlorocyclohexene- (3 In case (2) there may be mentioned as polyalcohols containing at least four hydroxyl groupsthe following:

Erythritol, xylitol, arabitol, sorbitol, mannitol, dulcitol, talitol, iditol, adonitol and pentaerythritol, heptitols, 2121626 tetramethylolcyclohexanol (1); also polyalcohols that additionally contain other functional groups, for example sugars, such as glucose, galactose, mannose, fructose, sucrose and the like; sugar acids such as glucoronic acid, galacturonic acid, mucic acid and the like. Finally, there may be used as polyalcohol a polymer containing free hydroxyl groups, such as a polysaccharide and more especially polyvinyl alcohol or partially hydrolysed polyvinyl acetate. The acetalization may follow the usual pattern and consists for example, in heating an aldehyde of the formula H (V) together with the diol or polyol in the presence of an acid catalyst, such, for example, as hydrochloric or paratoluenesulfonic acid.

This procedure yields at first an unsaturated acetal of the formula Y CPI-0:011

I: I 0 X1 X2 11 (VI) To obtain the acetals of the Formula II an alcohol of the formula ZOH is added in a second stage on to the double bond of the unsaturated acetal IV. As a rule, the alcohol Z'-OH contains an epoxidizable group. There may be mentioned chlorohydrin, for example a-methylglycerola-monochlorohydrin, fi-methylglycerolu-monochlorohydrin, glycerol-fi-monochlorohydrin, glycerol-a-bromohydrin and more especially glycerol-Demonochlorohydrin as well as mixtures of such monochlorohydrins, for example the commercial mixture of glycerolfl-monochlorohydriu and glycerol-a-monochlorohydrin; furthermore unsaturated alcohols such as allyl alcohol, crotyl alcohol, octadecenyl alcohol, A -cyclohexanol-1,

in which R to R each represent monovalent substituents such as halogen atoms, alkoxy groups or aliphatic, cycloaliphatic, araliphatic or aromatic hydrocarbon radicals, more especially lower alkyl groups containing 1 to 4 carbon atoms, or hydrogen atoms, in which formula R and R together may also constitute an alkylene radical such as a methylene group. As examples of such alcohols VII there may be mentioned: A -tetrahydrobenzyl alcohol, 6- methyl-A -tetrahydrobenzyl alcohol, 2 :4 6-trimethyl-A tetrahydrobenzyl alcohol, 1:5-endomethylene-M-tetrahydrobenzyl alcohol and 4-chloro-A -tetrahydrobenzyl alcohol.

When the unsaturated acetal VI is derived from an unsaturated polyol (n in Formula VI is preferably=1), x mols (x=not a whole number) of such an acetal can be added on to 1 mol of a polyhydroxy compound containing x hydroxyl groups.

As such polyhydroxy compounds there are suitable above all aliphatic or cycloaliphatic diols or polyols such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycols, propanediol, polypropyleneglycols, butanediol, pentanediol, hexanediol; glycerol, 1:1:1-trimethylolpropane, sorbitol, mannitol, pentaerythritol; quinitol, resorcitol.

This procedure gives rise to epoxidizable acetals, for example of the type (Gzradical of the diol) that is to say that the radical Z in Formula II is a radical of the formula As relevant examples may be mentioned the adducts of 2 mols of the acetal of acrolein and 1: l-bis-(hydroxymethyl)-cyclohexene-3 with 1 mol of a glycol or polyglycol such as ethylene glycol.

Instead of a diol or glycol there may be used water for the additive reaction of 2 mols of an unsaturated acetal VI derived from an unsaturated diol, whereby a simple ether of the formula is obtained, that is to say that the radical Z in the For- Inula II is in this case a radical of the formula Furthermore, 1 to (x-l) mols of an unsaturated acetal VI derived from an unsaturated diol may be added on to 1 mol of a polyhydroxy compound containing at hydroxyl groups. The free hydroxyl group(s) of the resulting adduct can then be further reacted with compounds containing in addition to epoxidizable groups such groups as can be condensed wtih hydroxyl groups, for example carboxyl or hydroxyl groups, halogen atoms or the like.

Thus, for example, in a first stage 1 mol of the acetal of acrolein and 1:l-bis-[hydroxymethyl]-cyclohexene-3 can be added on to 1 mol of a glycol or polyglycol, and in a second stage the resulting adduct is etherified, for example, with 1 mol of epichlorohydrin or A -tetrahydrobenzyl alcohol or dihydrodicyclopentadienol or esterifled with 1 mol of N-tetrahydrobenzoic acid.

When the radical of the polyol contains additionally at least one epoxidizable group, acetals of the Formula II are also obtained when in a second stage an alcohol of the formula Z'-OH or ZOH which as such contains an epoxide group, is added on. As examples of such alcohols may be mentioned glycidol or more especially epoxidized hydroaromatic alcohols of the formula such as 3:4-epoxy-hexahydrobenzyl alcohol.

By subjecting such an alcohol ZOH containing an epoxide group to an additive reaction wtih an acetal III there are obtained by the variant B of the present process directly the new epoxides of the Formula I. However, in this case the radical of the polyol no longer contains any epoxidizable groups; it contains either an epoxide group or is free from epoxide groups. The former is the case when the radical is that of a diol, the latter in general when the radical is that of a polyol containing at least four hydroxyl groups.

The additive combination of the alcohol Z-OH or ZOH with the carbon-to-carbon double bond of the aldehyde radical is advantageously carried out in the known manner, in the presence of a basic catalyst, such as sodium hydroxide, or more especially of an acid catalyst or a Lewis acid, such as sulfuric acid or boron trifluoride.

According to the variant A of the present process the acetal II, which still contains at least one epoxidizable group such as an epoxidizable carbon-to-carbon double bond or a halohydrin group, is treated with an epoxidizlng agent.

The epoxidation of the carbon-to-carbon double bond yielding the compound of the present invention is carried out by a conventional method, preferably with the aid of an organic per-acid, such as peracetic, perbenzoic, peradipic, monoperphthalic acid or the like. Another suitable epoxidizing agent is hypochlorous acid; when this substance is used HOCl is added on to the double bond in a first stage, whereupon in a second stage, by treatment with a hydrogen chloride donor, for example a strong alkali, the epoxide group is formed.

In correspondence with what has been said above with respect to the meaning of the term radical containing an epoxidizable group, the treatment according to the-v invention with the epoxidizing agent includes also the. treatment with an agent capable of splitting 01f hydrogen: halide (such as potassium hydroxide or sodium hydroxide) of halohydrin groups, for example the glycerol-- monochlorohydrin group, with formation of the corresponding 1:2-epoxide group or of a glycidyl group.

When the acetal II contains epoxidizable carbon-to carbon double bonds as well as halohydrin groups, the such, for example, as dicarboxylic anhydrides, into clear,

epoxidation is performed in two stages: advantageously, bright, cured products having excellent technical propthe carbon-to-carbon double bonds are first epoxidized erties, more especially an outstandingly high thermal and the halohydrin groups are then converted into stability according to Martens.

epoxide groups. 5 Similarly valuable technical properties are also found The epoxidation may lead, in addition to the diepoxides in the diepoxide compounds of the formulae or polyepoxides respectively, to wholly or only partially hydrolysed epoxides stemming from side reactions, that OH is to say compounds in which the epoxide groups of the R R polyepoxide I have been wholly or partially hydrolysed 2 2 to hydroxyl groups. 0 CH2 0 C The present invention is based on the observation that H CH crnmcHmm-cfi c 0 in general the presence of such lay-products has a favourfi X able elfect on the technical properties of the cured poly- 2 1 2 epoxides; accordingly it is in general of advantage not to '7 isolate the pure polyepoxide from the reaction mixture. R7 0 R4 The epoxidized acetals of the present invention may 4 also contain, of course, other functional groups, depend- (XIII) ing on the polyols and on the alcohols Z--0H from which they are derived. More especially, there may be present and in addition to the acetalized hydroxyl groups of the polyol, free hydroxyl groups so that certain properties, n such as the adhesivity or hydrophilicity or the curing OH 2 speed of the epoXrde compounds of the lnvention can be modified extensively. OH; /OCH.', /Cz

Particularly advantageous properties are found in the OH on I oHooH-oI-n-orr 0 CH diepoxides of the general formula I K i IV-CH on Ra\ /o\ /R9 /OCH o\ /R3 fi C CCH -O--CH-CH;CH o 0 XIV o R8 in 0-011: I i o 0 (]-R7 in Which the radicals X R and R to R have the same meanings as in Formulae XI and XII. R7 Further distinguished by their advantageous properties R5 R0 (XI) are the polyepoxide compounds of the general formula R1 R Rz\ /R1 I 2 I R3 0 R9 0 0 Re\\ /C\ /R3 \C/ \CCHZ-OCH-CHZO A oHCH,-orroOH,-o o 0 R3 O O Xi R8 0 \i 124 0 R1 R1 O R' Ra R5 in which X stands for a methyl group or for a hydrogen in which X and X each stand for hydrogen atoms or atom, and R to R and R to R each stand for monomethyl groups and the radicals R to R and R to R valent substituents such as halogen atoms or aliphatic, have the same meanings as in Formula XI and R has cycloaliphatic, araliphatic or aromatic hydrocarbon radithe same meaning as R and A represents a tetravalent cals, more especially for alkyl radicals with 1 to 4 carbon aliphatic radical which contains at least four carbon atoms, or for hydrogen atoms, and in Which R and R atoms, none of which has more than a single free together or R and R together may also form an alkylvalence; the aliphatic radical A may be unsubstituted or ene radical such as a methylene group. substituted, for example, by hydroxyl, ether, sulfide, car- Most readily available are the diepoxide compounds boxyl, carboxylic acid ester groups, keto, aldehyde, acetal of the formula groups or the like.

In an important special case the radical A may be E substituted by more than 2, for example, 3, 4 or more, CH CH-CHgOOHCHg-CH C CH acetal groupingsof the formula 0 i ii] o-0H2 o R2 R1 H CHR R-CH OH R3\ /0\ /R9 /0- oz ofiz (XII) /C O'CI'IZ O ?H C\,H\:Z in which X represents a hydrogen atom or a methyl I X1 group, and R and R each represent a hydrogen atom or C a lower allryl radical.

The epoxides defined above are bright, viscid or fusible resins which can be converted with suitable curing agents R5 R 7 8 Also in this case there are most readily accessible the radical which may be interrupted by oxygen atoms; and diepoxide compounds of the formula p =l or 2.

CH 0 CH 0% OHOH OCHOH OQ A CHCHz-CH-OOH;,HC OH 0 X, 0 o X l o \CH GR RCI-I C/H Cfig Cfig (XVI) in which X; and X each stand for hydrogen atoms or The most advantageous manner of preparing these methyl groups, R and R for hydrogen atoms or lower preferred diepoxide compounds of the Formulae XI,

alkyl groups, and A for a tetravalent saturated aliphatic XII, XV or XVIII is to react an epoxidizing agent on a hydrocarbon radical which may be substituted by at most hydroaromatic acetal of any one of the formulae two hydroxyl groups and which contains 4, or 6 carbon R2 R1 atoms, none of which contains more than a single free I valence, and furthermore no hydroXyl groups may be K bound to carbon atoms having such a free valence. O CCH;O-OH-OH -CH C C The epoxides constitute bright, fusible resins which I I OCHz can be converted with suitable curing agents, for ex- I ample dicarboxylic anhydrides, into clear, bright, cured C C products havlng excellent technical properties. R4 0 R1 R1 0 R4 Furthermore, there may be mentioned in this connecr l tion triepoxide compounds of the formula XX f5 0 )3 /CH GHCHaO-CHCHz-Cfi A %OHCH2CIJHOCH2CH Cg O\[ 1 \O/A\O XI /0 CH /CHR O\ /O RC{I CH OH, OH 0 2 $11, &HX1"

$11, 5 0X2 CH-R H /(EH3 C]E[ (XVII) in which X X and X each stand for hydrogen atoms OH R R or methyl groups, R, R and R" for hydrogen atoms or 2 lower alkyl-radicals, and A" represents a hexavalent satu- H 3H i H; OCH2 0 R3 rated aliphatic hydrocarbon radical which contains 6 Al CH l carbon atoms, none of which has more than a single l free valence. CH O CH The properties of these last-mentioned epoxides re- Ra7C\ semble those of the epoxides of the Formula XVI. 0

Products that likewise have a considerable practical 4 importance are the diepoxide compounds of the general 5 formulae (XXI) R: R1 BK /Rg R3 0 CHg-O /OCH2 /C\ /R3 C \O/ GHCH CHO%GO}-(FHCH -OE /C c\ 0 I GHQO X, X1 0-0112 '/0 7% R4 C\ R7 R7 /C\ 4' Ra Ra Ra R5 (XVIII) and /oH /OH -0 OCH;\ /C I\ /CH C\ CI-ICH (|3HO |:GO] (I3HCH$Cs /0 CH o orn-o Xi H X1 0-011, 0 CH /C]E[R RCH /ofi CH, OH

(XIX) in which the radicals X X R to R and R to R have the same meanings as in the Formulae XV and XVI; G represents an aliphatic or cycloaliphatic hydrocarbon in Which X X R to R R to R A, G and p have the same meanings as in Formulae XI, XIII, XV, XVIII. The acetals of the Formulae XX and XXI are obtained in the simplest manner as follows:

Acrolein or crotonic aldehyde is acetalized with a diol IV, whereby an acetal of the formula is obtained which is then subjected to an additive reaction with a hydroaromatic alcohol of the formula VII or with dihydrodicyclopentadienol-S, whereby the acetal XXIV is obtained.

The acetals of the Formula XXII are easiest to prepare in the following manner:

Acrolein or crotonic aldehyde is acetalized with a polyol which contains at least 4 hydroxyl groups, whereby a spirocyclic acetal of the formula X1 o 0 X1 (XXV) is obtained, of which 1 mol is added on to 2 mols of a hydroaromatic alcohol of the Formula VII.

In a similar manner there can be prepared the derivatives of dihydrodicyclopentadienol by adding on to 2 mols thereof 1 mol of acetal XXV.

The acetals of the Formula XXIII are easiest to prepare by an additive reaction of 2 mols of an acetal XXIV with 1 mol of water (p l) or 1 mol of a diol of the formula HOGOH (p=2).

Instead of first preparing a hydroaromatic acetal of the Formula XX or XXII and treating it with an epoxidizing agent, the diepoxide compounds of the Formula XI or XV are also obtained by adding an epoxidized hydroaromatic alcohol X on to an acetal XXIV or XXV.

The epoxidized acetals of the present invention react with the conventional curing agents for epoxide compounds; with the aid of such curing agents they can be cross linked or cured in the same manner as other polyfunctional epoxide compounds or epoxy resins. Suitable relevant curing agents are basic or more especially acidic compounds.

Good results have been achievedwith amines or amides, such as aliphatic and aromatic primary, secondary and tertiary amines, for example monobutylamine, dibutylamine, tributylamine, para-phenylenediamine, bis-[paraaminophenylJ-methane, ethylcnediamine, NzN-diethylenediarnine, N:N-dimethylpropylenediamine, diethylene- 75 triamine, tetra- [hydroxyethyl] -diethylenetriamine, tri ethylenetetramine, tetraethylenepentamine, trimethylamine, diethylamine, triethanolamine, Mannichs bases, piperidine, piperazine, guanidine and guanidine derivatives such as phenyldiguanidine, diphenylguanidine, dicyandiamide, aniline-formaldehyde resins, urea-formaldehyde resins, melamine formaldehyde resins, polymers of aminostyrenes, polyamides, for example those of aliphaticpolyamines and dimerized or trimerized unsaturated fatty acids, isocyanates, isothiocyanatesg.polyhydric phenols, for example resorcinol, hydroquinone, bis-[4-hydroxyphenyl1- dimethylmethane, quinone, phenolaldehyde resins, oilmodified phenolaldehyde resins, reaction products of aluminum alcoholates or phenolates with compounds of tautomeric reaction of the type of the acetoacetic ester, Friedel-Crafts catalysts, for example aluminum chloride, antimony pentachloride, tin tetrachloride, zinc chloride, boron trifluoride and complexes thereof with organic compounds, metal fluoborates, boroxines, or phos phoric acid. Preferably used curing agents are polybasic carboxylic acids and anhydrides thereof, for example phthalic anhydride, methylendomethylene-tetraa hydrophthalic anhydride, dodecenyl-succinic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, hexachlonoendomethylene-tetrahydrophthalic anhydride or endomethylene-tetrahydrophthalic anhydride,

or mixtures thereof; maleic or succinic anhydride; if desired, accelerators may be used additionally, such as tertiary amines or strong Lewis bases, such, for example, as alkali metal alcoholates, and advantageously polyhydroxy compounds such as hexanetriol, or glycerol.

It has been observed that in curing the epoxy resins of the invention with carboxylic anhydrides it is of advantage to use for every gram equivalent of epoxide groups only about 0.3 to 0.9 gram equivalent of anhydride groups. When a basic accelerator is used, such as an alkali metal alcoholate or an alkali metal salt of a carboxylic acid, up to 1.0 gram equivalent of anhydride groups may be used.

The term curing as used in this connection refers to the conversion of the epoxide compounds described above into insoluble and infusible resins.

Accordingly, the present invention also provides curable mixtures containing'the epoxidized acetals according to the invention as well as curing agents for epoxy resins, preferably an anhydride of a dicarboxylic or polycarboxylic acid.

The curable mixtures of the present invention further contain with advantage at certain share of otherwise suitable acetals whose epoxide groups, however, are wholly or partially hydrolysed to hydroxyl groups and/or other polyhydroxy compound-s displaying a cross-linking action, such as hexanetriol. It will be readily understood that. the curable epoxide compounds may also contain other epoxides such, for example, as monoor polyglycidyl ethers of monoor polyalcohols such as butanol, 1:4- butanediol or glycerol, or of monoor polyphenols such as resorcinol, bis-[4-hydroxyphenyl]-dimethylmethane or condensation products of aldehydes with phenol (novo laks); furthermore polyglycidyl esters of polycarboxylic acids such as phthalic acid, and also aminopolyepoxides such as are obtained, for example, by dehydrohalogenating a reaction product of an epi-halohydrin with a primary or secondary amine, such as n-butylamine, aniline or 4:4- dimonomethylamino) -diphenylmeth ane.

The curable epoxide compounds or mixtures thereof with curing agents may also be treated before the curing at any desired phase with a filler, plasticizer, coloring matter or the like. Suitable extenders and fillers are, for example, asphalt, bitumen, glass fibers, mica, quartz meal, cellulose, kaolin, finely dispersed silicic acid (Aerosil) or metal powders.

The mixtures of the new epoxide compounds and ouring agents can be used With or without fillers, if desired in the form of solutions or emulsions, as textile assistants, laminating resins, paints, lacquers, dipping resins, casting resins, coating compositions, pore-fillers, putties, adhesives, moulding compositions or the like, as well as for the manufacture of such products. The new resins are particularly valuable as insulating compounds for the electrical industry.

In the following examples parts and percentages are by weight, the relationship between parts by Weight and parts by volume being the same as that between the kilogram and the liter.

EXAMPLE 1 (a) Acetal of acrolein and 1:1-bis-[hydroxymethyl1- cyclohexene-S A mixture of 118 parts of acrolein, 286 parts of 1:1- bis- [hydroxymethyl]-cyclohexene-3 and 3 parts by volume of sulfuric acid of 50% strength is heated for 20 minutes at 50 C. When all has passed into solution, 700 parts by volume of benzene and 2 parts of para-toluenesulfonic acid are added and the whole is boiled for 40 minutes in a circulation distillation apparatus until 40 parts of water have distilled over azeotropicallly. The solution is treated with 4 parts of anhydrous sodium carbonate, filtered and evaporated. The benzene is distilled off at 54-61 C. under a pressure of 0.2 mm. Hg, and 319 parts of acetal (3 vinyl 2:4 dioxospiro( :5 )-undecene-9) pass over which corresponds to a yield of 87% of the theoretical. There remain 40 parts of an unidentified residue.

(b) Additive reaction with A -tetrahydrobenzyl alcohol A mixture of 225 parts of the acetal described above (3-vinyl-2:4-dioxospiro(5:5)-undecene-9), 140 parts of A -tetrahydrobenzyl alcohol, 0.5 part by volume of concentrated sulfuric acid and 0.5 part by volume of a solution of 50% strength of boron trifluoride in diethyl ether (boron trifiuoride'present in the form of its etherate) is heated to 80 C and then allowed tocool. There are obtained 360 parts of a brown liquid in which tetrahydro benzyl alcohol can no longer be detected; it consists substantially of 3-[A -tetrahydrobenzyl-hydroxyethyl] -2:4-dioxospiro( 5 5 -undecene-9.

(c) Epoxidation 320 parts of the above 3-[A -tetrahydrobenzyl-hydroxyethyl] -2 4-dioxospiro- 5 z 5 -undecene-9 (crude product) are dissolved in 1000 parts by volume of benzene and 25 parts of sodium acetate are added. In the course of 20 minutes 462 parts of per-acetic acid of 39.5% strength are stirred in in portions, While maintaining the temperature at about 35 C. by intensive cooling. When the mixture has reacted for another 2 hours at 30 C. with stirring, the reaction is complete and the reaction mixture is cooled to room temperature. Titration reveals that the theoretical amount of peracetic acid has been consumed.

The benzene solution is washed three times with 300 parts by volume of water and then with aqueous sodium hydroxide solution until it is neutral and washed twice more with 150 parts by volume of water. The benzene solution is dried over sodium sulfate, filtered and evaporated under reduced pressure. The last remnants of the solvent are expelled in a high vacuum at 100 C. There are obtained 317 parts of a pale-yellow liquid resin containing 5.3 epoxide equivalents per kg. and having a vis cosity of about 25,000 centipoises at 20 C., it consists substantially of the diepoxide of the formula 0 lares; CHr-O CHz-CH on oHo1n-on,-o-on, on

err-0H, GHQ-O on,on, 0

EXAMPLE 2 (a) Acetal of acrolein and 1:1-bis[hydr0xymethyl]-6- methylcycl0hexene-3 A mixture of 56 parts of acrolein, 157 parts of 1:1- bis-[hydroxymethyl]-6-methylcyclohexene-3 and 1 part of sulfuric acid of 50% strength is heated in a water bath at 40 C. until all has passed into solution. An exothermic reaction sets in so that after removal of the water bath the temperature rises to 50 C. 350 parts by volume of benzene are then added and the mixture is boiled for 40 minutes in a circulation distillation apparatus until 20 parts of water have passed over azeotropically. The solution is treated with 2 parts of anhydrous sodium acetate, filtered and evaporated. The benzene is distilled off under a vacuum of 0.5 mm. Hg at 81 C. and 163 parts of acetal [3-vinyl-7-methyl-2z4- dioxospiro(5 :5)-undecene-9] pass over which corresponds to a yield of 83.6% of the theoretical. There remain 27 parts of an unidentified residue.

(b) Additive reaction with A -tetrahydrobenzyl alcohol A mixture of 65 parts of the above acetal [3-vinyl-7- methyl-2:4-dioxospiro(5 :5 )-undecene-9], 38 parts of A tetrahydrobenzyl alcohol, 0.5 part of concentrated sulfuric acid and 0.5 part of a solution of 40% strength of boron trifluoride in diethyl ether (boron trifluoride present as the etherate) is heated for 4 hours at C., left to itself for 15 hours, and then shaken with 2 parts of anhydrous sodium carbonate, to yield 101 parts of a liquid in which tetrahydrobenzyl alcohol can no longer be detected; it consists substantially of 3-[A '-tetrahydrobenzylhydroxyethyl] -7-methyl-2 :4-dioxospiro (5 :5 -undecene-9.

(c) Expoxidation A solution of 97 parts of the above 3[A -tetrahydrobenzyl hydroxyethyl] 7 methyl 2:4 dioxospiro- (5:5 )-undecene-9 in 280 parts by volume of benzene is treated with 7 parts of anhydrous sodium acetate and in the course of 30 minutes 148 parts of peracetic acid of 39.5% strength are stirred in dropwise, while maintaining the temperature at 30-35 C. by external cooling. After 2 hours 91% of the theoretical amount of peracetic acid have been consumed. After 3 hours the reaction mixture is allowed to cool to room temperature, the aqueous bottom phase is separated and the supernatant phase washed three times with 100 parts by volume of water on each occasion, then neutralized by being shaken with 100 parts by volume of water containing 7 parts by volume of sodium hydroxide solution of 30% strength, then washed twice with 50 parts by volume of water on each occasion, dried over sodium sulfate, filtered and evaporated at 100 C. under a pressure of 0.15 mm. Hg. There are obtained 774 parts of a liquid, paleyellow resin containing 4.5 epoxide equivalents per kg. and having a viscosity of 27,474 centipoises at 20 C 13 This resin consists substantially of the diepoxide of the formula (a) Acetal of crotonic aldehyde and 1:1-bis-[hydr0xymethyl1-cycl0hexene-3 A mixture of 70 parts of crotonic aldehyde, 143 parts of 1:l-bis-[hydroxymethyl]-cyclohexene-3 and 08 part 14 EXAMPLE 4 An acetal is prepared as described in the preceding examples from 107 parts of crotonic aldehyde and 229 parts of 1: l-bis- [hydroxymethyl]-6-methylcyclohexene-3 in the presence of 1 mol of sulfuric acid of 50% strength and of benzene for the azeotropic distillation of the reaction water. When the reaction mixture is fractionated under vacuum, 270 parts of 3-propenyl-7-n1ethyl-2:4-dioxospiro(5:5)-undecene-9 pass over at 75-82 under 0.2 mm. Hg.

A mixture of 158 parts of this acetal, 75 parts of 6- methyl-A -tetrahydrobenzyl alcohol and 1.5 parts of a soluti0n-0f 40% strength of boron trifluoride in diethyl ether is heated for 2 hours at 80 C. After 30 parts of y vqlume 0f Sulfuric i of Strength is heafted for 15 forerunnings have been distilled off at 140 C. under 0.1 3.3. 211fil fiiiniifgafiii if rfi i iiii lii i lii fii i" i 5 f fi fi" E? 2 i Fi i 0 m su stantia o t e a uct o "me' y-A -era ybenzene are added and the whole is boiled for 30 minutes dmbenzoylgxy 2' propyl 7 methyl 2;4 di in a circulation distillation apparatus until 18 parts of 20 spir0-(5:5)-ImdeCeI1-9. Water have passed over azeotropically. The solution is A i t of 215 parts f thi adduct and 600 parts treated With 2 Parts Of anhydrou? q t acetate, filtered by volume of benzene is treated with 16 parts of sodium and evaporated- The benzene 1S d1S'E11 1ed Off at acetate; while continuously stirring the mixture, 249 under Hg and are Qbtalned 180 Parts of parts of peracetic acid of 42% are added in portions at 366ml P p y 214 P l C. After 2 hours the theoretical amount of peracetrc corfespondlng to 92% 0f the thfiofetlcal yleld. acid has been consumed, and the reaction mixture is then (b) Addition reaction with M-tetrahydrobenzyl alcohol z f l ogf g g fi l ig Yifi' ora 1011 a un er mm. g yre s a rig m 5 5 Paras of g lg s g viscid resin containing 4.7 epoxide equivalents per kg. g gggs g g g g ig z g bJ y gi fii id gg 30 whilch consists substantially of the dlepoxide of the foracid of 50% strength is heated for 8 hours at 80 C., mu a then left to itself for 15 hours, and freed from unreacted CH O tetrahydrobenzyl alcohol by evaporation under vacuum, a g 19 parts of the alcohol passing over at C. under 0.15 35 I mm. Hg. The residue amounts to 253 parts, correspondcg CH CHQ-CH-O-CHQ;OH /OH ing to a yield of crude product of 92% consisting substantially of 3[A -tetrahydrobenzoyloxy-(2')-propyl]-2:4-di- CH: OHTO H3 CH3 CH CH2 oxospiro (5 5 -undecene-9. O

A I t f 253 ')t f g li 3 3 h d 40 anfd cirlr be cured with phthalic anhydride to form a pale,

so u 101'! 0 par so e a ove A "-tetra y roin u-si e resin. benzoyloxy (2') propyl] 2:4 dioxospiro(5:5) undecene-9 in 750 parts by volume of benzene is treated with EXAMPLE 5 20 parts of anhydrous sodium acetate, and in the course of 45 minutes 340 parts of peracetaic acid of 39.9 A mixture of 22 parts of the cyclic acetal of 2 mols itrellgtht are it 3 8d3 grogwrseE whllle mirlntalnifgfgt th; of acrolein and 1 mol of pentaerythritol-referred to as empfira We a Y ex @1118 9 3:9-divinyl-spiro-bi-[meta-dioxane] or as 3:9-diviny1- hours the theoretical amount of peracetic acid has been g;4;g; i 5; 5 d d 22 parts f iiiiluif aQZZZEZ ZJEJAiE ESSJ$$Z$3$ii2 t -ra e r i at su one am 0 s ren an ar 0 a so n 1011 Supernatant Phase Washed thfeefimfis With 150 p by of 40% strength of boro trifluon'de in diethyl ether. g i j f h li q t h i gg t f i thenf neuttl'ahled The mixture is heated for 12 hours at 80 C., after which 3{ P 5 a 61! W1 P 5 Y V0 ume O er 9 time a viscid, yellowish brown product has formed in 2 35 7 Parts EV 201111113 1 1 S0d11 1m hYdTOXIde Solutlon which tetrahydrobenzyh alcohol can no longer be de- 0 3 strengt t 611 was ed f f 100 P by tected and whlch consists substantially of the adduct 213112111: fervgaltirngizvzgghagg:ilsgofidodrgdmoggr l giiq rg 3:9 b(i1s [A tetrahydrobenzyl-hydroxyethyl1-spiro-bime a- 1oxane Hg in the course of 30 minutes. There are obtained 774 A Solution of 45 parts of the above adduct in 140 parts of a viscid yellow resin containing 5.1 epoxide parts by volume of benzene is treated with 4 parts of P g g t ggi g and having a Vlscoslty of 102,700 centl' sodium acetate. In the course of 15 minutes, 40 parts of P01S peracetic acid of 42.8% strength are stirred in dropwise. Tl'llS resin consists substantlally of the d1epox1de of the While maintaining the temperature at by cooling formula with ice. The mixture is then stirred for another 60 min- 0 utes at 30 C. and the aqueous bottom phase is sepa- CHFO CHFO ratetd.b Thel benzerfre solution is Evashedtwice1 with 50 par s y vo ume o wa er on eac occasion, me over E fi /CH CHZ CHTOCHTCH sodium sulfate and evaporated, to yield a viscid resin. CH-C 2 CI-Ir-O H3 GET-CH2 containing 2.70 epoxide equivalents per kg. This resin 7 consists substantially of the diepoxide of the formula 0 0 CH-Cgg /OCHg CH30 CHaCfi CE /CHCHz-OCH;OH;C$ /O CHOHgCHg-OCH2OH CH cur-CH2 O-OH; CHr-O CH -Ofi and can be cured with phthalic anhydride to form a bright, infusible resin.

EXAMPLE 6 A mixture of 91 parts of the cyclic triacetal of 3 mols of acrolein and 1 mol of sorbitol, 105 parts of A -tetrahydrobenzyl alcohol and 0.5 part of a solution of 45% strength of boron trifluoride in diethyl ether is heated for 5 hours at 80 C., allowed to cool, and parts of unreacted tetrahydrobenzyl alcohol are then distilled out of the mixture at C. under 0.15 mm. Hg. Thus, the residue consists of an adduct of exactly 2 mols of the alcohol and 1 mol of the triacetal. This adduct is epoxidized in the following manner:

A solution of 153 parts of the residue described above in 350 parts by volume of benzene is treated with 7 parts of sodium acetate. In the course of 35 minutes, 134 parts of peracetic acid of 35.8% strength are stirred in dropwise, while maintaining the temperature at 3035 C. by cooling with ice. When the mixture is stirred for another 60 minutes at 30 C., the theoretical amount of peracetic acid has been consumed. The mixture is allowed to cool and the aqueous bottom phase is separated. The benzene solution is washed twice with 100 parts by volume of water on each occasion and once with 100 parts by volume of aqueous 2 N-sodium hydroxide solution, then washed twice with parts by volume of water, dried over sodium sulfate, filtered and evaporated under 0.5 mm. Hg pressure, finally at 100 C. There are obtained 159 parts of a yellow, viscid resin containing 2.1 epoxide equivalents per kg. This resin can be cured with phthalic anhydride to form a bright, 4 infusible resin.

EMMPLE 7 A mixture of 23 parts of glycerol-a-monochlorohydrin and 36 parts of the acetal prepared as described in Example 1 from acrolein and l:1-bis-[hydroxymethy1]- cyclohexene-3 is treated with 0.5 part of a solution of 40% strength of boron trifluoride in diethyl ether and heated for 80 minutes at 80 C. r

The cycloolefinic double bond in the resulting adduct 3 [2' hydroxy 3 chloropropoxyethyl] 2:4 dioxospiro(5:5)-undecene-9is epoxidized in the following manner:

The completely reacted reaction mixture described above (about 59 parts) is treated with 150 parts of benzene and 5 parts of anhydrous sodium acetate. While stirring and cooling with ice 36 parts of peracetic acid of 42.8% strength are added dropwise within 30 minutes at 30 C., and the mixture is then stirred on for 60 minutes at 30 C., after which time the theoretical amount of peracetic acid has been consumed and the mixture is then worked up as described in the preceding examples, to yield 52 parts of monoepoxidized chlorohydrin.

The resulting monoepoxide is converted into a diepoxide in the following manner:

The 52 parts of the above epoxidized chlorohydrin- 3 [2' hydroxy 3' chloropropoxyethyl] 9:10 epoxy-2:4-dioxospiro(5 :5) undecane-are treated with 27 parts of aqueous sodium hydroxide solution of 28% strength and the whole is heated for one hour at 50 C. 100 parts of benzene are then added and the precipitated :solid sodium chloride is filtered off. The benzene layer is separated, washed until neutral and finally evaporated in a high vacuum, to yield 42 parts of a pale-yellow, liquid 1 6 epoxy resin consisting substantially of the diepoxide compound of the formula With the aid of phthalic anhydride it can be cured to form a practically colorless, infusible resin.

EXAMPLE 8 A mixture of 45 parts of glycerol-winonochlorohydrin and 43 parts of the cyclic acetal of 1 mol of pentaerythritol and 2 mols of acrolein3:9 divinyl spiro bi [meta-dioxane]-is treated with 0.5 part of a solution of 45% strength of boron trifluoride. For 15 minutes a weakly exothermic reaction can be observed, after the completion of which free g1ycerol-u-monochlorohydrin can no longer be detected in the reaction mixture. The whole is then allowed to cool, treated with 63 parts of aqueous sodium hydroxide solution of 28% strength and heated with vigorous stirring for one hour at 45 C. The solid sodium chloride is then filtered off, the henzene solution is separated and evaporated, to yield as residue 70 parts of a viscid pale-yellow resin containing 1.8 epoxide equivalents per kg. which consists substantially of the diepoxide of the formula OCH CHr-O and can be cured with phthalic anhydride to form an infusible resin which is only slightly tinted.

EXAMPLE 9 Impact bending strength cm. kg./sq. cm.

Bcndin g strength kg./sq. mm.

A second portion of each of the above mixtures is cast in a layer about 0.1 mm. and 1 mm. thick on plates of glass and then cured for 24 hours at 140 C. The films cured in this manner adhere excellently to the support and are resistant towards 5 N-sulfuric acid, 5 N-sodium hydroxide solution, water, acetone and chlorobenzene after exposure thereto for one hour at room temperature.

EXAMPLE 10 parts of the polyepoxy resin prepared as described in Example 1 are mixed at room temperature with 11.9 parts of 2:4-dihydroxy-3-hydroxymethylpentane, and in this mixture 51 parts of phthalic anhydride are dissolved at -125 C. as curing agent. When, as described in Example 9, this mixture (about 90 grains) is cast in aluminum moulds it gels at 120 C. within about one hour, that is to say that the originally liquid mixture has 1 7 solidified to form a gel. After having been cured for 24 hours at 140 C. the casting displays an impact bending strength of 12.7 cm. kg./ sq. cm. and a bending strength of 16.0 kg./sq. mm.

EXAMPLE 11 51 parts of phthalic anhydride (0.65 equivalent of anhydride groups per equivalent of epoxide groups) are dissolved at 120 to 130 C. in 100 parts of a polyepoxy resin prepared as described in Example 1. At 120 C. the mixture has a viscosity below 10 centipoises and after 2% hours of 1500 centipoises. The mixture is cast in aluminum moulds as described in Example 9. Curing is carried out in two stages, first for 24 hours at 140 C. and then for 24 hours at 200 C. The resulting casting has an outstandingly high thermal stability of over 235 (measured according to Martens DIN).

EXAMPLE 12 5.94 parts of a sodium alcoholate prepared by dissolving 0.41 part of sodium metal at about 120 C. in 100 parts of 2:4-dihydroxy-3-hydroxymethylpentane are dissolved at room temperature in 100 parts of the epoxy resin prepared as described in Example 1. 1.0 equivalent of phthalic anhydride per equivalent of epoxide groups is fused in as curing agent at 120-125 C. A first portion of the mixture is cast in aluminum moulds as described in Example 9 and cured for 24 hours at 140 C. The resulting casting has the following properties:

Impact bending strength 13.6 cm. kg./ sq. cm. Bending strength M 14.8 kg./sq. mm. Thermal stability according to Martens DIN 166.

Another portion of the above mixture is used for cementing tests in which degreased and ground strips of aluminum (170 x 25 x 1.5 mm.; overlap 10 mm.) marketed under the trade name Anticorodal B are cemented together. The curing of the cemented joint is carried out for 24 hours at 140 C.

At different test temperatures the following tensile shear stresses are obtained:

Test temperature Tensile shear strength in C.: kg./sq. mm.

Room temperature 1.05 100 0.92 150 0.88 170 0.80 190 0.82

As is shown by this table the cemented joints display excellent tensile shear strengths, above all at the extremely high test temperature of 150-190 C.

EXAMPLE 13 100 parts of the polyepoxy resin prepared as described in Example 3 are fused together with 45.6 parts of phthalic anhydride as curing agent at 120-125, 0.6 equivalent of anhydride groups being used for every equivalent of epoxide groups of the resin. The mixtures are cured in an aluminum mould (40 x x 140 mm.) for 24 hours at 150 C. The casting cured in this manner has an impact bending strength of 13.9 cm. kg./sq. cm. and a bending strength of 10.1 kg./sq. mm.

EXAMPLE 14 2.5 parts of a boron trifluoride/monoethylamine complex are dissolved in 50 parts of the polyepoxy resin prepared as described in Example 3. The mixture is cast in an iron mould and cured for 16 hours at 150 C. The resulting casting has a thermal stability of 138 (measured according to Martens DIN).

EXAMPLE 15 A mixture of 86 parts of ethylene glycol and 550 parts of the acetal obtained according to Example 1(a) from 1:l-bis-[hydroxymethyl]-cyclohexene-3 and acrolein (3- vinyl-2z4-dioxospiro-5:5-undecene9) is heated to C., and 1 part of concentrated sulfuric acid is stirred in, whereupon the temperature rises slightly. The reaction mixture is then heated for 2 hours at -90 C., at first with slight cooling and after the evolution of heat has subsided by heating on an oil bath. The acid is then neutralized with 2 parts of sodium carbonate, and 41 parts of excess acetal, passing over at 550 C. under 0.3 mm. Hg, are distilled out of the reaction mixture. The ethylene glycol has reacted completely. The resulting distillation residue consists of 578 parts of crude ethylene glycolbis-[2-(2r4 dioxospiro 5'25) undecene-9'-yl-(3)- ethyl]-ether in the form of a pale-brown oil.

The 578 parts of the adduct described above are taken up with 1700 parts by volume of benzene, 30 parts of anhydrous sodium acetate are added and the mixture is heated to 35 C. In the course of 30 minutes 555 parts of peracetic acid of 41.3% strength are then added dropwise while maintaining a temperature of 35 C. which is kept up for another 2 hours after the whole of the oxidizing agent has been added dropwise. At first the reaction mixture must be slightly cooled for about 1 /2 hours and after that this temperature is maintained by heating. After the indicated time the theoretical amount of oxidizing agent has been consumed.

The whole is then cooled and the aqueous phase is separated. The benzene layer is Washed three times with 400 parts by volume of water on each occasion, 120 parts of sodium hydroxide solution of 30% strength being added to the third washing water in order to neutralize any remaining acetic acid. The layer is then washed once more with 200 parts by volume of water, the solvent is distilled off under a partial water-jet vacuum and the residue is freed from last remnants of volatile constituents by being heated at 100 C. under 0.1 mm. Hg. In this manner there are obtained 563 parts of a pale-yellow oil which contains 4.18 epoxide equivalents per kg. of the theoretical content) and consists substantially of the compound of the formula (EH 0 O CH:

CHCH2CH2O CH2CH2O CH2CH2CH /O 32 /CH CH7 0 OCH l C EXAMPLE 16 198 parts of the acetal described in Example 1(a) of acrolein and l:l-bis-[hydroxymethyl]-cyclohexene-3 are heated with 38 parts of trimethylene glycol to 80 C. and 0.5 part of concentrated sulfuric acid is added, whereupon a slight increase in temperature is observed. As described in Example 15, the reaction mixture is then maintained for 2 hours at 85-90" C., and then treated with 1 part of sodium carbonate, whereupon 18 parts of excess acetal are caused to pass over under a pressure of 0.2 mm. Hg, to leave 210 parts of trimethylene glycol-bis-[2-(2:4'-dioxospiro-S 5 -undecene-9'-yl-( 3 -ethyl] -ether in the form of a viscous, yellow oil which is epoxidized by taking ,it up with 600 parts by volume of benzene, adding 1 part of anhydrous sodium acetate and dropping in 198 parts of 40.7% peracetic acid in the course of 30 minutes at '35 C. After having stirred the mixture for a further ture is maintained for-3 hours at 8590 C. and the reaction mixture is then neutralized with 1 part of anhydrous sodium carbonate. 20 parts of excess acetal are then distilled off in a high vacuum to yield as residue 349 parts of pentanediol bis [2 (2'24 dioxospiro- 5':5) undecene 9' yl (3) ethyl] ether in the form of a dark, viscous liquid.

These 349 parts are taken up in 1050 parts by volume of benzene, treated with 16 parts of anhydrous sodium acetate and epoxidized, as described in Example 15, with 309 parts of peracetic acid of 40.7% strength. Working When this product is cured with phthalic anhydride as described in Example 15, a flexible, solid, infusible resin is obtained.

EXAMPLE 17 A mixture of 46 parts of 1:4-butanediol and 200 parts of the acetal described in Example 1(a) of acrolein and 1:l-bis-[hydroxymethyl]-cyclohexene-3 is heated to 80 C., and 0.5 part of concentrated sulfuric acid is added, whereupon the temperature rises slightly. While stirring the mixture thoroughly the temperature is maintained for 2 hours at 8590 C., at first with slight cooling and after the evolution of heat has subsided by heating. 1 part of anhydrous sodium carbonate is then added and 20 parts of excess acetal are distilled off at 50 C. under 0.3 mm. Hg, which corresponds exactly to the initially added excess. There remain as distillation residue 223 parts of butanediol bis [2-(2':4'-dioxospiro-5':5')- undecene 9' yl (3' ethyl] ether in the form of a dark, viscous oil.

The latter oil is epoxidized in the following manner: The crude product is taken up in 600 parts by volume of benzene, 10 parts of anhydrous sodium acetate are added and in the course of 30 minutes at 35 C. 196 parts of peracetic acid of 40.8% strength are added dropwise. The oxidation is carried on for another 3 hours and the desired temperature of 35 C. is maintained first by slightly cooling and later on by heating. After the indicated time 98.5% of the theoretical amount of oxidizing agent have been consumed. Further working up is carried out as described in Example 15. After having removed the last traces of volatile constituents in a high vacuum there are obtained in this manner 233 parts of a viscous, yellow liquid which contains 3.95 epoxide equivalents per kg. (94.5% of the theoretical content) and consists substantially of the diepoxide of the formula up is performed as described in Example 15. There are finally obtained 362 parts of a viscous, yellow liquid containing 3.84 epoxide equivalents per kg. (95.3% of the theoretical content).

EXAMPLE 19 A mixture of 198 parts of the acetal described in Example 1(a) of acrolein and 1:1 bis [hydroxymethyl] cyclohexene 3 and 100 parts of polyethyleneglycol (average molecular weight 200) is heated to C., 1 part of concentrated sulfuric acid is added and the temperature is maintained for 2 hours at 90 C.; after neutralization with 1 part of anhydrous sodium carbonate 17 parts of excess acetal are distilled off under 0.2 mm. Hg pressure, to yield as residue 270 parts of a viscous, brown liquid.

Said liquid is taken up in 800 parts by volume of henzene, treated with 10 parts of anhydrous sodium acetate and epoxidized with 198 parts of peracetic acid of 40.8% strength. After washing and concentration there are obtained 273 parts of a viscous, yellow liquid containing 3.24-epoxide equivalents per kg. (95.9% of the theoretical content).

EXAMPLE 20 A mixture of 298 parts of the acetal of acrolein and 1:1- bis-[hydroxymethyl]-cyclohexene-3 and 225 parts of a polyethylene glycol of average molecular Weight 300 is heated to 80 C. After addition of 1 part of sulfuric acid and 0.5 part of boron trifiuoride etherate (48% strength) no rise in temperature is observed. The tem perature is then maintained by heating for 3 /2 hours at 85-90 C. and the mixture is then neutralized and 23 parts of excess acetal are distilled off, to leave 492 parts of a viscous, brown liquid.

Said liquid is taken up with 1470 parts by volume of When this product is cured for 24 hours at 140 C. with phthalic anhydride (0.7 equivalent of anhydride groups per equivalent of epoxide groups), a pale-yellow, flexible, solid, infusible resin is obtained.

EXAMPLE 18 A mixture of 87 parts of pentanediol-1:5 and 298 parts of the acetal described in Example 1(a) of acrolein and 1:1 bis [hydroxymethyl] cyclohexane 3 is heated to 80 C., 1 part of concentrated sulfuric acid is added,

benzene, treated with 16 parts of anhydrous sodium acetate and epoxidized with 310 parts of peracetic acid of 40.8% strength for 3 hours at 35 C., whereby of the theoretical amount of oxidizing agent are consumed. After washing, neutralization and concentration there are obtained 418 parts of a viscous, pale-yellow liquid containing 2.84 epoxide equivalents per kg. which, after having been hardened for 24 hours at C. with phthalic anhydride (0.65 equivalent of anhydride groups per equiv- Whereupon the temperature rises slightly. The tempera- 7 5 alent of epoxide groups), forms a flexible, infusible resin.

21 EXAMPLE 21 A mixture of 279 parts of the acetal of acrolein and 1zl-bis-[hydroxymethyl]-cyclohexene-3 and 319 parts of polypropylene glycol (average molecular weight 425) is heated to 85 C. and treated with 1 part of concentrated sulfuric acid, whereby no heating up occurs. 0.5 part of boron trifluoride etherate of 40% strength is then added, whereupon th temperature rises very slightly and is maintained for 6 hours at 85-90 C. After neutralization with 3 parts of sodium carbonate and distilling off the excess acetal, there remain 586 parts of a viscous, dark liquid.

The latter liquid is taken up in 1500 parts by volume of benzene, treated with 14 parts of anhydrous sodium carbonate and epoxidized with 284 parts of peracetic acid of 44.2% strength. The theoretical amount of oxidizing agent is consumed. After working up as described in Example 15 there are obtained 585 parts of a very viscous, yellow liquid containing 2.17 epoxide equivalents per kg. (89% of the theoretical content).

Curing of this product with phthalic anhydride (one equivalent of anhydride groups per equivalent of epoxide groups) furnishes a very flexible and plastic casting.

EXAMPLE 22 369 parts of the acetal of acrolein and 1: l-bis-[hydroxyrnethyl]-cyclohexene-3 and 106 parts of transquinitol are heated to 80 C., the quinitol passing only partially into solution. Upon addition of 1 part of sulfuric acid a slight rise in temperature is observed and the remainder of the quinitol dissolves slowly. The temperature is maintained for 3 hours at 9095 C. and the reaction mixture is then cooled whereupon it crystallizes.

458 parts of the resulting crude mixture are dissolved in 1200 parts by volume of benzene and 20 parts of anhydrous sodium carbonate are added. The mixture is then heated at 35 C. and in the course of 30 minutes 390 parts of peracetic acid of 43.4% strength are added dropwise, whereupon the mixture is stirred on for 2 hours at the same temperature, cooled, the aqueous layer is separated and the benzene layer is worked up as described in Example 15. There are obtained 427 parts of a slightly tinted compound which crystallizes on cooling and contains 3.72 epoxide equivalents per kg. (94.2% of the theoretical content).

When this product is cured for 24 hours at 140 C. with phthalic anhydride (one equivalent of anhydride groups per equivalent of epoxide groups) castings are obtained which have good mechanical properties.

EXAMPLE 23 A mixture of 217 parts of the acetal prepared as described in Example 3(a), consisting of 1:1-bis-[hydroxymethyl]-cyclohexeue-3 and crotonic aldehyde, and 31 parts of ethylene glycol is heated to 80 C. and then treated with 2 parts of sulfuric acid, whereupon no heating up occurs. The mixture is then heated on an oil bath to 105 C., whereupon a slightly exothermic reaction sets in. The temperature is maintained for a further 2 hours at 105 C., whereupon 2 parts of sodium carbonate are added and 15 parts of excess acetal are distilled off, to leave 227 parts of a viscous, dark liquid.

The latter liquid is taken up with 660 parts by volume of benzene, treated with 18 parts of anhydrous sodium carbonate and epoxidized With 216 parts of peracetic acid of 39.5% strength as described in Example 15. Working up as described in Example 15 yields 211 parts of a very viscous, orange-colored liquid containing 3.75 epoxide equivalents per kg. (90.5% of the theoretical content).

EXAMPLE 24 A mixture of 276 parts of the acetal of acrolein and 1:l-bis-[hydroxymethyl]-cyclohexene-3 and 225 parts of dihydrodicyclopentadienol-8 is heated to 85 C. and 0.5

22 part of sulfuric acid of 98% strength is added, whereupon the temperature rises spontaneously. The temperature is maintained for 24 hours at 90 C., at first by cooling and then by heating. The resulting adduct is then epoxidized in the following manner:

The adduct is treated with 1350 parts of benzene and 35 parts of sodium acetate and then heated to 35 C. In the course of 30 minutes 576 parts of peracetic acid of 43.6% strength are then added. The temperature is maintained for another 2% hours at 35 C., at first by cooling and then by heating. The product is then washed, neutralized and concentrated as described in Example 1(a), to yield finally 505 parts of a viscous, yellow liquid containing 5.15 epoxide equivalents per kg. (93.3% of the the.- oretical content) which consists substantially of the compound of the formula The latter product is cured with phthalic anhydride (0.7 equivalent of anhydride groups per equivalent of epoxide groups) for 24 hours at 140 C., to form a bright, yellow, infusible resin having a thermal stability of 180 (Martens, DIN) and possessing good mechanical properties.

EXAMPLE 25 A mixture of 268 parts of octadecenyl alcohol and 186 parts of the acetal described in Example 1(a) of acrolein and l:1-bis-[hydroxymethyl]-cyclohexene-3 is heated to C. and 0.5 part of sulfuric acid of 98% strength is added, whereupon slight heating up occurs. The temperature is maintained for 3 hours at C. 1 part of sodium carbonate is then added and the mixture is heated to C. under 0.2 mm. Hg which causes no distillation. The adduct obtained in this manner is a viscous, yellow liquid.

The latter product is epoxidized in the following manner: 1150 parts of benzene and 20 parts of sodium acetate are added and the mixture is heated to 35 C., whereupon within 20 minutes 384 parts of peracetic acid of 43.5% strength are added; the temperature is then maintained for 2% hours at 35 C., after which time the theoretical amount of oxidizing agent has reacted. The product is washed, neutralized and concentrated at a final temperature of C. under 0.1 mm. Hg. There are obtained 458 parts of a viscous, yellow liquid containing 3.64 epoxide equivalents per kg. When this product is cured for 24 hours at with phthalic anhydride (0.7 equivalent anhydride groups per equivalent of epoxide groups) it forms a bright, yellow, flexible and infusible resin.

EXAMPLE 26 A mixture of 22.5 parts of water and 450 parts of the acetal described in Example 1(a) of acrolein and 1:1-bis- [hydroxymethyl]-cyclohexene-3 is heated to 80 C. and then treated with 3.5 parts of para-toluenesulfonic acid, whereupon the temperature rises slightly and the reaction mixture begins to boil under reflux. The boiling point rises gradually and reaches after 5 hours 90 C. at a bath temperature of 102 C. At this point the bulk of the water has reacted. The acid is then neutralized with 5 parts of sodium carbonate, and 3 parts of water and 4 parts of unreacted acetal are distilled oil, to leave 461 parts of his [2 2':4 dioxospiro-S':5)-undecene-9'-yl- (3)-ethyl]-ether in the form of a dark oil. Determination of the content of double bonds by hydrogenation reveals 98.5% of the theoretical content.

.566 parts of the resulting unsaturated ether acetal are taken up in 15 30 parts of benzene, 35 parts of sodium acetate are added and the mixture is heated to 35 C. and

then treated Within 30 minutes with 580 parts of peracetic acid of 43.2% strength. The temperature is maintained for 2% hours at 35 C., at first by cooling and then by heating. The aqueous layer is separated and the benzene layer is washed, neutralized and concentrated as described in Example 1, to yield 420 parts of a highly viscous, yellow product containing 4.40 epoxide equivalents per kg. and consisting substantially of the diepoxide of the formula ized with parts of anhydrous Na CO and the reaction product subjected to tractional distillation. There are obtained at 52-94 C. under 0.15 mm. of pressure of mercury 260 parts of unreacted ethylene glycol, at 125-130 C. under 0.15 mm. of pressure of mercury 500 parts of unsaturated alcohol (3-hydroxyethoxyethyl-2:4-dioxospiro-(5:5)-undecene-9) and as residue 230 parts of the addition product of 2 moles of acetal and 1 mol of ethylen glycol.

The resulting unsaturated alcohol is converted into the corresponding chlorhydrin as follows: CH: 0112.0 0.0112 CH: 363 parts of the above described 3-hydroxyethoxyethylfl \CHOmCHflOGILCEhOt/I 2:4-dioxospiro-(5:5)-undecene-9 and 1 part of borontri- CH fluoride etherate of 40% strength are heated at 80 C. t 153 parts of epichlorhydrin are added dropwise in the H 2 H2 011 course of 15 minutes to the well stirred mixture, care Q, being taken that a temperature of 8085 C. is maintained, if necessary by cooling. Stirring is then continued at the same temperature for 30 minutes. At the end of Aft h i b d i h h h li h d id 6 this time no unreacted starting material is detectable. 515 equivalent of anhydride groups per equivalent of epox- Parts Of a Viscous Yellow liquid are Obtainedide groups) for 24 hours at 170 C. it forms a bright, The resulting chlorhydrin is epoxidized as follows: infusible resin having very good mechanical properties. The resulting 515 Parts of chlorhydrin are dissolved in 1390 parts of benzene, 20 parts of anhydrous sodium EXAMPLE 27 acetate are added and 219 parts of peracetic acid of 43.2%

strength are added dropwise in the course of 30 minutes at A mixture of 90 parts of 3-vinyl-2:4-dioxospiro(5 :5 C. with cooling. Stirring is continued for 3 hours. 'undecene-9 (acetal from A -cyclohexene-1:l-dimethanol Th aqueous layer i then separated, the organic phase and flcfoleih), 90 Parts Of the Diels-Aldel addllct 0f washed and neutralized and the solvent evaporated in an butanediol with hexachlorocyclopentadiene and 0.5 part 30 analogous manner to h d ib d i h preceding by volume of concentrated sulfuric acid is heated for 4 amples, There are obtained 486 parts of a yellow viscous hours at 80 C. The solid Diels-Alder adduct slowly di liquid containing 2.63 epoxide equivalents per kg. (92% solves. When the reaction is complete, a highly viscous f th th o ti al yi ld), liquid is obtained which does not contain any starting ma- The resulting reaction product is then dehydrohaloge terial. 5 ated as follows:

The so-obtahled Product is dissolved in 430 Parts of 479 parts of the resulting epoxidized product are vigorbenzene and, after the addition f 5 parts f anhy ously stirred with 365 parts of sodium hydroxide solution sodium acetate, epoxidized with 87 parts of peracetic acid f 30% strength for 1 hours at 50 55C, 800 parts of of 43.6% strength at 35 C. as described in the preceding benzene are then added, the aqueous layer is separated examples- The reaction requires for completion 3 hours 40 and the benzene distilled off from the organic layer under at 35C. The OXidated r a ti n pr du t i W rk d up in reduced pressure, the vacuum being increased to 0.1 mm. an analogous manner to that described in the preceding pressure of mercury at 100 C. temperature of the botexamples. There are obtained 152 parts of aproduct crystom roduct, There are finally obtained 403 parts of a tallized in the cold which contains 2.1 epoxide equivapale yellow mobile liquid containing 5.5 epoxide equivalents P 8- and Which consists chiefly 0f the diepOXide lents per kg. (86.5% of the theoretical yield) which consists chiefly of the diepoxide of the formula CH, 011 -0 /OH CH-CH CH OCHg-OH -O-CH -CH-OH, O I CHa-O CH CH, cg of the formula Diepoxide with similar properties are obtained, when CH2 in the above Example 28 the 434 parts of ethylene glycol C1 fi are replaced by an equivalent amount of diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene O I glycol, 1,3-propylene glycol, 1,4-butanediol 1,5-pentane Ol-O on-cnro-orn-om-on 0 on diol or 1,6-hexanediol.

o-on ofi, 0 What is claimed is: o1o01 1. A diepoxy compound of the formula 0-011, 01-1, 01- l OH-CHa-O-CHz-CHr-CH O \OH 0 o-oni 0 R1 on, on o-cn, /o\

Cgr7CHCHzL0-G -l-O?H-(?H=CH o o The product can be cured with an acid anhydride, such as n 1 X1 X1 O-CH; I o phthalic anhydride, to form sparingly combustible 0r RFC incombustible castings.

1 C 4 EXAMPLE 28 A mixture of 630 parts of 3-vinyl-2z4-dioxo-spiro- (5 :5)-undecene-9, 434 parts of ethylene glycol and 4 parts of paratoluene sulfonic acid is heated for 90 minutes at in which X represents a member selected from the class C. The mixture is then cooled, the acid is neutralconsisting of hydrogen atom and the methyl group, X

25 26 is hydrogen and in which R and R are selected from the 2. The diepoxide of the formula group consisting of hydrogen, halogen, lower alkyl, and CH2 together R and R form the methylene group, R R 2 R R R and R each represents a member selected CET7CH-CHPO OHFCHPC{I from the class consisting of a hydrogen atom, a halogen 5 0 0-011, I J O atom and lower alkyl, G is the divalent hydrocarbon ob- CH 2 tamed by removing the termlnal hydroxyl groups from an aliphatic saturated dialcohol with two to six carbon CH1 atoms, and n is an integer of at least 1 and at the most 2. 3. The diepoxide of the formula O-GHn CH; 037CH-CH oCHz-oHz-0CH2CH2(JE /0 O O-CH; l l/O No references cited.

WALTER A. MONDANCE, Primary Examiner.

CERTIFICATE OF CORRECTION Patent No. 3,210,375 October 5, 1965 Daniel Porret et ale It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 1, line 42, for "groups" read group line 69, for "1:2 epoxide" read lz2-epoxide column 2, line 35, for trimethylcyclohexne" read trimethylcyclohexenecolumh 4, lines 7 and 35, for "wtih", each occurrence, read with columns 7 and 8, formula XVI, the extreme lefthand portion of the formula should appear as shown below instead of as in the patent:

column 12, line 21, for "bis[hydroxymethyl] in italics,

read bis-[hydroxymethyl] in italics; line 55, for 3[A tetrahydro-" read 3 [A -tetrahydro column 13, line 45, for "39.9%" read 39.5% column 14, lines 32 to 38, the extreme right-hand portion of the formula should appear as shown below instead of as in the patent:

O CH same column 14, line 62, for "dropwise read dropwise, column 18, line 18, for "550 Ct read 55 C" column 19, line 39, for "(3" read (3) columns 19 and 20,

lihes 58 to 62, the extreme right-hand portion of the formula should appear as shown below instead of as in the patent:

column 22, lines 17 to 23, the last portion of the formula should appear as shown below instead of as in the patent:

CH CHCH CH2 I /T CH CH-CH-O column 24, line 2, for "tractional" read fractional same column 24, lines 59 to 71, for that portion of the formula reading CH= read CH- Signed and sealed this 21st day of June 1966.

(SEAL) Attest:

ERNEST W. SWIDER EDWARD J. BRENNER slttesting Ufficer Commissioner of Patents 

1. A DIEPOXY COMPOUND OF THE FORMULA 